CN102304206B - The method preparing the dispersion of polymer particle of surfactant-free insensitive for pH in aqueous medium - Google Patents
The method preparing the dispersion of polymer particle of surfactant-free insensitive for pH in aqueous medium Download PDFInfo
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Abstract
The invention provides a kind of dispersion of polymer particle in an aqueous medium and manufacture a kind of its method, this dispersion include polymer that a kind of emulsion is polymerized and be covalently bonded to the polymerization of this emulsion polymer on a kind of macromole evocating agent.This active macromolecules initiator includes the monomer a kind of hydrophilic, that pH is insensitive being in the form reacted.By making at least one monomer and this active macromolecules initiator carry out reacting and there is no surfactant to complete this or polyreaction of these monomers, it is possible to obtain this dispersion of polymer particle.The polymer of this emulsion polymerization can be to include at least one other ethylene linkage unsaturated monomer being in the form being polymerized.
Description
Invention field
The present invention relates to a kind of dispersion of polymer particle in an aqueous medium and manufacture a kind of its method.
Background of invention
During dispersion of polymer particle or emulsion are used for much applying, such as binding agent, paint, paper coating, textile coating etc..Emulsion polymerization is typically used for being formed a type of Raolical polymerizable of the dispersion of polymer beads, and this dispersion is typically by a kind of emulsion mixed with water, at least one monomer and one or more surfactants.In conventional emulsion polymerization, surfactant is the most critical, because surfactant provides the site of particulate nucleation (i.e. monomer swell micelle), controls latex particle size and the polymer beads by being formed provides colloidal stability.But, for the application of a lot of latex, Small molecular surfactant has some shortcomings.Such as, Small molecular surfactant can to the high water sensitivity (causing blush) of film transfer and can in film formation process desorption (reducing from surface nature and final performance).
But, in terms of the effective emulsion polymerization that need not surfactant is provided, there have been latest developments.nullSuch as，American Chemical Society's original copy (Macromolecules 2009 in entitled " Nitroxide-Mediated Controlled/LivingFree-Radical Surfactant-Free Emulsion Polymerization of MethylMethacrylate Using a Poly (methacrylic acid)-Based MacroalkyoxyamineInitiator [the Controlled/Living free radical surfactant-free emulsion polymerizations of the NO free radical regulation and control of the methyl methacrylate using one to carry out based on poly-(methacrylic acid) macromole alkoxyamine initiator] " of Charleux et al.，42，In 95-103)，Describe in the emulsion polymerization of a kind of surfactant-free, use some macromole evocating agent.Specifically, describe one to be used in a kind of surfactant-free, batch emulsion polymerization as a kind of active macromolecules initiator based on poly-(methacrylic acid) polymer such as poly-(methacrylic acid-copolymerization-styrene).
It has been found, however, that the emulsion polymerization such as employing macromole evocating agent based on acrylic acid, methacrylic acid-copolymerization-styrene or methacrylic acid-copolymerization-styrene sulfonic acid sodium salt requires that this latex has an alkaline pH.This is because the emulsion of a kind of low pH may cause instability and the solidification of latex during synthesizing or shortly after that, especially under higher solids content.
Summary of the invention
The many aspects of the present invention include the pH sensitivity eliminating or reducing latex and allow it under all pH value, especially keep stable under low ph value (e.g., less than 7).The present invention includes the species specific macromole evocating agent to this polymer emulsion transmission pH insensitivity.Due to this improvement, it is not necessary to pH to be maintained at a specific alkalescence value (the most not requiring a kind of buffer agent).Therefore, the invention provides and use the insensitive macromole evocating agent of a kind of pH and for the controlled free-radical emulsion polymerization of surfactant-free to manufacture high solid, a kind of sane method of stable dispersion of polymer particle.
According to one embodiment of the invention, a kind of dispersion of polymer particle in an aqueous medium includes polymer that a kind of emulsion is polymerized and a kind of macromole evocating agent, and this macromole evocating agent includes being in the form reacting (being such as polymerized), the monomer a kind of hydrophilic, that pH is insensitive being covalently bonded on the polymer of this emulsion polymerization.The polymer of this emulsion polymerization includes at least one other ethylene linkage unsaturated monomer being in the form being polymerized.
According to another embodiment of the invention, a kind of active macromolecules initiator has formula R-{ [(A)x(B)y]-Y}n Or 1, wherein A is a kind of hydrophilic, monomer that pH is insensitive, and B is a kind of comonomer, and Y is an end group, x >=1, y >=0, and n >=2, and wherein A and B can in any order or order occurs；And R has with following formula (I) or (III):
Wherein R1And R3Identical or different, represent the alkyl of straight or branched that a carbon number having is from 1 to 3；R2Represent a hydrogen atom, a carbon number having from the alkyl of straight or branched of 1 to 8, a phenyl, an alkali metal ion or an ammonium ion；And Z represents an aryl or one there is formula Z1-[X-C(O)]nGroup, wherein Z1Representing a kind of polyfunctional structure, wherein X is an oxygen atom, a nitrogen-atoms with a carbon-based group, a hydrogen atom or a sulphur atom.Such as, R can be a dimethyl carboxylic group, and Y can be to have with the R ' of following formula (II).
More specifically, R ' can be N-tert-butyl-n-(1-diethylphosphoryl base-2,2-dimethyl propyl) NO free radical.
According to another embodiment of the invention, this active macromolecules initiator and at least one monomer reaction is made to have formula R-{ [(A) to form onex(B)y]-[(C)m]p-Y}n Or 1Polymer, wherein A is this monomer hydrophilic, that pH is insensitive, and B is a kind of comonomer, C is the undersaturated monomer of at least one ethylene linkage, and Y is an end group, x >=1, y >=0, m >=1, n >=2, and p >=1, if wherein p ＞ 1, the most each C section has a kind of different composition, and A and B can occur in this active macromolecules initiator in any order or sequence, and R has with following formula (I) or (III):
Wherein R1And R3Identical or different, represent the alkyl of straight or branched that a carbon number having is from 1 to 3；R2Represent a hydrogen atom, a carbon number having from the alkyl of straight or branched of 1 to 8, a phenyl, an alkali metal ion or an ammonium ion；And Z represents an aryl or one there is formula Z1-[X-C(O)]nGroup, wherein Z1Representing a kind of polyfunctional structure, wherein X is an oxygen atom, a nitrogen-atoms with a carbon-based group, a hydrogen atom or a sulphur atom.
According to another embodiment of the invention, a kind of method for manufacturing dispersion of polymer particle includes making at least one monomer react with a kind of macromole evocating agent and not having surfactant to complete being polymerized of this at least one monomer, and wherein this macromole evocating agent includes that the monomer hydrophilic, that pH is insensitive of a kind of form being in and being polymerized and this at least one monomer are at least one ethylene linkage unsaturated monomer.
According to another embodiment of the invention, a kind of method forming latex includes making a kind of monomer hydrophilic, that pH is insensitive and a kind of alkoxyamine compound including a nitrogen-oxygen key carry out being reacted to form a kind of macromole evocating agent.Being prepared for a kind of water-based emulsion, this emulsion includes at least one monomer and this active macromolecules initiator, but not including that surfactant.This emulsion is kept under the polymerization conditions to provide a kind of latex comprising scattered polymer beads.
Detailed description of the invention
The many aspects of the present invention include dispersion of polymer particle in an aqueous medium and active macromolecules initiator, these active macromolecules initiators comprise a kind of for prepare dispersion of polymer particle, be in the form being polymerized, monomer insensitive for pH.
As used herein, " latex ", " latex " and " dispersion of polymer particle " can be used interchangeably to contain any polymer beads known to those skilled in the art, and it may be at a kind of stable aqueous colloidal suspension liquid, emulsion or dispersion or the form of these polymer beads separated with this.
As used herein, unless otherwise indicated, the value of these compositions or component is the percentage by weight with each composition or % by weight represents.All values up includes until the end points that is given and include these end points provided herein.
In one embodiment of the invention, a kind of dispersion of polymer particle in an aqueous medium includes polymer that a kind of emulsion is polymerized and a kind of macromole evocating agent, and this macromole evocating agent includes being in the form reacted, monomer a kind of hydrophilic, that pH is insensitive on the polymer that is covalently bonded to the polymerization of this emulsion.The polymer of this emulsion polymerization includes at least one other ethylene linkage unsaturated monomer being in the form being polymerized, such as (methyl) acrylate, styrene, (methyl) acrylamide, (methyl) acrylonitrile and their mixture.
This dispersion of polymer particle includes the macromole evocating agent of a kind of form being in and reacting or be polymerized.Therefore, when describing monomer, skilled artisan will appreciate that is this macromole evocating agent one or more monomers of including being in the form reacted.In other words, the repetitive in this polymer is referred to as " residue " forming the monomer of this repetitive.These polymer can be straight chain, side chain, crosslinking etc. or their any combination.These polymer can be homopolymer (being i.e. made up of a type of monomer) or copolymer (being made up of the monomer of two or more types).These monomeric units of copolymer can in block, the most randomly, statistically arrange, gradient or their any combination.Gradient polymer include its structure or constitute be not macroscopically homogeneity but become with position in the sample multiple multicomponent polymeric.Will be described below this for the method manufacturing macromole evocating agent.
This is controlled during (or activity) radical polymerization, this macromole evocating agent is used as initiator, stabilizer and/or controlling agent.This macromole evocating agent extends the amphiphilic block copolymer creating self assembly in position with the chain of multiple ethylene linkage unsaturated monomer, forms activity micelle.Along with the continuation of living polymerization, these activity micelles become the polymer beads of self-stabilization, it is not necessary to the surfactant of any routine.After chain extends, this macromole evocating agent is no longer active, but final dispersion of polymer particle is active, thus allows the synthesis of polymer architecture complicated in the emulsion polymerization of surfactant-free.
This active macromolecules initiator includes a kind of monomer hydrophilic, that pH is insensitive or polymer.As used herein, " hydrophilic " and " water miscible " can be used interchangeably, for being described in a kind of aqueous medium a kind of monomer that can easily dissolve.Specifically, this monomer can comprise a hydrophilic molecules or its part, and it is charge polarization and can carry out hydrogen bonded.This active macromolecules initiator is that pH is insensitive and be not responding to the change of pH in medium around.Such as, insensitive for a kind of pH monomer or polymer will not the swelling or shrinkages in response to the change of pH.Specifically, no matter pH how, and holding is water miscible by monomer or polymer that effective pH is insensitive.
This active macromolecules initiator can include any the most water miscible and that pH is insensitive monomer or polymer.Monomer insensitive for the most hydrophilic and pH can include those with a substituent group in the following or function/degree of functionality :-OH, CO2H、SO3H, ammonium, phosphono (such as-PO3H), epoxide, amino, amide and their salt.
This active macromolecules initiator can include non-ionic monomer, anionic monomer, cationic monomer and have a kind of anionic nature and the ampholytic monomer of a kind of cationic property in a molecule.Non-ionic monomer can classification by kind be that pH is insensitive generally.Suitably non-ionic monomer may include that such as NVP, acrylamide and Methacrylamide and their derivant and acrylic acid and the derivant of methacrylic acid.Anionic monomer can be pH insensitive and can to include being in the form being polymerized time those more Plus acidic than poly-(acrylic acid).Additionally, the insensitive monomer of suitable pH can include the acid monomer with low pKa.As for one of those skilled in the art it is apparent that the definition of " low pKa " can change based on the functional group's (such as sulphonic acid ester, phosphate ester etc.) in this monomer.Such as, suitable anionic monomer can be selected from having a sulfonic acid group or the acrylic acid of a phosphate group and methacrylic acid, maleic acid, maleic anhydride or acrylate and methacrylate.
In an exemplary embodiment, this active macromolecules initiator can include a kind of monomer among 2-acrylamido-methyl propane sulfonic acid (AMPS) and salt, vinyl benzyl phosphonic acids and salt thereof, DMAA, hydroxyethyl acrylate, glycidyl methacrylate, siloxanes functional monomer and their mixture.
This active macromolecules initiator can include at least one water miscible salt of a kind of monomer, this monomer be in be polymerized form, include an acryloyl group (H2C=CH-C (=O)-) and a sulfonic acid group (-S (=O)2-OH).Specifically, this includes that the monomer of an acryloyl group and a sulfonic acid group can be 2-acrylamido-methyl propane sulfonic acid (AMPS).
This monomer can include a kind of water miscible salt.It is, for example possible to use a kind of monovalent cation such as sodium, lithium, potassium and ammonium form this salt.It is thus possible, for instance a kind of water miscible AMPS salt can include AMPSNa, AMPSLi, AMPSK, AMPSNH4, etc..In an exemplary embodiment, this monomer is 2-acrylamide-2-methylpro panesulfonic acid sodium salt or vinyl benzyl Alendronate.Under the form reacted, this monomer residue can be expressed as " p " or " polymerization " (such as pAMPSNa).
This active macromolecules initiator being in the form being polymerized can have a following chemical formula:
R-{[(A)x(B)y]-Y}n Or 1,
Wherein A is a kind of hydrophilic, monomer that pH is insensitive, and B is a kind of comonomer, and Y is an end group, x >=1, y >=0, and n >=2, and wherein A and B can in any order or order occurs；And R has with following formula (I) or (III):
Wherein R1And R3Identical or different, represent the alkyl of straight or branched that a carbon number having is from 1 to 3；R2Represent a hydrogen atom, a carbon number having from the alkyl of straight or branched of 1 to 8, a phenyl, an alkali metal ion or an ammonium ion；And Z represents an aryl or one there is formula Z1-[X-C(O)]nGroup, wherein Z1Representing a kind of polyfunctional structure, wherein X is an oxygen atom, a nitrogen-atoms with a carbon-based group, a hydrogen atom or a sulphur atom.
Y can include any suitable end group, and this will be that those skilled in the art are readily determined.This end group can be from arbitrary end monomer unit of these monomers described here.In an exemplary embodiment, Y is R ', and it includes below formula (II):
In one embodiment, R is a dimethyl carboxylic group and R ' is N-tert-butyl-n-(1-diethylphosphoryl base-2,2-dimethyl propyl) NO free radical.
Such as, if A is AMPSNa, wherein x is 0 more than 1 (such as pAMPSNa) and y, and this macromole evocating agent can seem as follows, wherein should be ionized from the methacrylic acid segment of BB-MA:
Monomer insensitive for this pH is polymerized with a kind of alkoxyamine initiator (such as comprising a kind of initiator an of-N-O-key that can form NO free radical) and forms this active macromolecules initiator.By having to carry out a controlled radical polymerization of monomer that this is hydrophilic, that pH is insensitive in the presence of a kind of alkoxyamine compound of following formula (IV) or (V), a kind of active macromolecules initiator solution can be formed.
Wherein R1And R3It is same or different and represents the alkyl of straight or branched that a carbon number having is from 1 to 3.R2Represent a hydrogen atom, a carbon number having from the alkyl of straight or branched of 1 to 8, a phenyl, an alkali metal ion or an ammonium ion.Z represent an aryl or one there is formula Z1-[X-C(O)]nGroup, wherein Z1Representing a kind of polyfunctional structure, wherein X is an oxygen atom, a nitrogen-atoms with a carbon-based group, a hydrogen atom or a sulphur atom；And n >=2.
Preferably, this alkoxyamine initiator is a kind of alkoxyamine initiator based on NO free radical.A kind of suitably alkoxyamine based on NO free radical is N-(2-methyl-propyl)-N-(the 1-diethylphosphoryl base-2 with below formula; 2 ,-dimethyl propyl) azanol is (also referred to as-O-(2-carboxyl acrylate-2-yl)Or BB or BB-MA, can obtain in a branch company of Philadelphia, PA from Arkema Inc):
ShouldInitiator comprises a kind of NO free radical component; this component is to have N-tert-butyl-n-(the 1-diethylphosphoryl base-2 of below formula; 2-dimethyl propyl) NO free radical (also referred to as SG1 or SG-1 also can get from Arkema Inc.):
In order to control the reaction between this alkoxyamine compound and the insensitive monomer of this pH further, it is also possible to add a kind of secondary or other compound oxygen radical of nitrogen.Such as, during the controlled Raolical polymerizable of the monomer hydrophilic at this, pH is insensitive and this alkoxyamine compound, N-tert-butyl-n-(1-diethylphosphoryl base-2,2-dimethyl propyl) NO free radical (SG1) can be added.
Monomer that this is hydrophilic, that pH is insensitive or polymer can be with other comonomers (B) copolymerization.For example, it is possible to select other comonomers to modify the characteristic of this active macromolecules initiator or by requiring that less component sensitive for this pH reduces cost.Suitably comonomer (B) can be included in wide pH scope those still keeping anionic nature.Such as, this active macromolecules initiator can include with this is hydrophilic, the monomer of a kind of non-sulfonated of monomer copolymerization that pH is insensitive.10008 additionally or alternatively, this active macromolecules initiator can include with this is hydrophilic, a kind of sulfonation of monomer copolymerization that pH is insensitive or phosphorated monomer.
This dispersion of polymer particle includes the polymer (C) that a kind of emulsion is polymerized.The polymer of this emulsion polymerization can be to include at least one other ethylene linkage unsaturated monomer being in the form being polymerized.Such as, the polymer of this emulsion polymerization can be to include the one or more of monomers being in the form being polymerized, this monomer is selected from lower group, and the composition of this group is: (methyl) acrylate, styrene, (methyl) acrylamide, (methyl) acrylonitrile and their mixture.As used herein, name " (methyl) ", as those of ordinary skill in the art will recognize that, be intended as a kind of optional substituent group.In other words, (methyl) acrylate covers both acrylate and methacrylate.Additionally, name " acrylate ", " acrylamide " etc. are intended to contain the ester of this compound, salt and free acid, and they can serve as monomer described here.
Such as, suitable acrylate can include acrylic acid C1-C12Arrcostab.Acrylic monomers may include that such as acrylic acid or its salt, Arrcostab；Cycloalkyl or aryl-acrylic acid esters；Methyl, ethyl, butyl, ethylhexyl or phenyl acrylate；Hydroxyalkyl acrylates；2-hydroxy ethyl methacrylate；Ether alkyl acrylate；2-methoxyethyl acrylate；Alkoxyl or aryloxy group polyalkene glycol acrylates；Methoxy polyethylene glycol acrylate；Ethyoxyl polyethylene glycol acrylate, methoxyl group polypropylene glycol acrylate, methoxy poly (ethylene glycol)/polypropylene glycol acrylate or their mixture；Amino alkyl acrylates；2-(dimethylamino) ethyl propylene acid esters (DMAEA)；Amine salt acrylate；[2-(acryloxy) ethyl] trimethylammonium chloride or sulfate；[2-(acryloxy) ethyl] dimethyl benzyl ammonium chloride or sulfate；Acrylate, silylated acrylate or the phosphorous acrylate of fluorination；Such as aklylene glycol phosphate acrylate.Preferably monomer can include butyl acrylate, acrylic acid methyl ester., ethyl acrylate, butyl acrylate, 2-EHA, decyl acrylate, etc..
Such as, suitable methacrylate can include the C of methacrylic acid1-C12Arrcostab.Such as, these methacrylate monomer can include methacrylic monomer；Methacrylic acid or its salt；Alkyl, cycloalkyl, alkenyl or arylmethacrylate；Methyl, lauryl, pi-allyl or phenyl methacrylate；Hydroxyalkyl methacrylate；HEMA or methacrylic acid 2-hydroxypropyl ester, methacrylic acid ether Arrcostab；Methacrylic acid 2-ethoxyethyl group ester；Alkoxyl or aryloxy group poly alkylene glycol methacrylate；Methoxy polyethylene glycol methacrylate-styrene polymer, ethyoxyl polyethylene glycol methacrylate-styrene polymer, methoxyl group methacrylates, methoxy poly (ethylene glycol)/methacrylates or their mixture；Methacrylic acid aminoalkyl ester；Methacrylic acid 2-(dimethylamino) ethyl ester (MADAME)；Amine salt methacrylate；[2-(methacryloxy) ethyl] trimethylammonium chloride or sulfate and [2-(methacryloxy) ethyl] dimethyl benzyl ammonium chloride or sulfate, the methacrylate of fluorination；Methacrylic acid 2,2,2-trifluoro ethyl ester；The methacrylate of silylation；3-methacryloxypropyl trimethyl silane；Phosphorous methacrylate；Aklylene glycol phosphate methacrylate, hydroxyethyl imidazolines ketone methacrylate, hydroxyethyl ethylidene-urea methacrylate and methacrylic acid 2-(2-oxygen-1-imidazolidinyl) ethyl ester.
Suitably styrene can include that styrene, substituted phenylethylene (include C1-C4The substituted styrene of alkyl), Sodium styrene sulfonate and the styrene of halogenation, such as α-methylstyrene, 2-chlorostyrene, 4-chlorostyrene, bromostyrene, 2,5-dichlorostyrene and 4-methoxy styrene.Suitably acrylamide bag and methyl acrylamide monomer may include that such as acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide and N-t-octyl group (methyl) acrylamide.Suitably acrylonitrile and methacrylonitrile can also be selected by those skilled in the art.
This active macromolecules initiator and at least one monomer can carry out reacting and forming a kind of polymer with below formula:
R-{[(A)x(B)y]-[(C)m]p-Y}n Or 1,
Wherein A is this monomer hydrophilic, that pH is insensitive, and B is a kind of comonomer, and C is the undersaturated monomer of at least one ethylene linkage, Y is an end group, x >=1, y >=0, m >=1, n >=2, and p >=1, if wherein p ＞ 1, the most each C section has a kind of different composition, and A and B can occur in this active macromolecules initiator in any order or sequence, and R has below formula (I) or (III):
Wherein R1And R3Identical or different, represent the alkyl of straight or branched that a carbon number having is from 1 to 3；R2Represent a hydrogen atom, a carbon number having from the alkyl of straight or branched of 1 to 8, a phenyl, an alkali metal ion or an ammonium ion；And Z represents an aryl or one there is formula Z1-[X-C(O)]nGroup, wherein Z1Representing a kind of polyfunctional structure, wherein X is an oxygen atom, a nitrogen-atoms with a carbon-based group, a hydrogen atom or a sulphur atom.
Such as, Y can be to have with the R ' of following formula (II):
It is attached on the polymer of this emulsion polymerization at least one some covalent of this macromole evocating agent.In other words, this macromole evocating agent is all covalently bonded on the polymer of this emulsion polymerization is unnecessary.
In one embodiment of the invention, the polymer beads of these emulsions polymerization can include the homopolymer with the monomer of single type or have the copolymer of monomer of more than one type.These copolymers can be statistics, the random or copolymer of gradient.These copolymers can comprise one or more block selected from lower group, and the composition of this group is: pure (methyl) acrylic acid block, (methyl) acrylic acid block of mixing and (methyl) acrylic/styrene block of mixing.In one embodiment, the polymer of this emulsion polymerization includes butyl polyacrylate and polymethyl methacrylate.In another embodiment, the polymer of this emulsion polymerization includes butyl polyacrylate, polymethyl methacrylate and polystyrene.In still another embodiment, the polymer of this emulsion polymerization includes butyl polyacrylate, polymethyl methacrylate and polymethylacrylic acid.
This particle dispersion is in a kind of aqueous medium.Preferably aqueous medium is water, but other aqueous solvents include that polar aprotic solvents is also likely to be suitably.This water can be any suitable type, that such as distill, deionized, processed etc..The type of aqueous medium and amount are not particularly limited, but the amount that can use is to reach the granularity desired by enough emulsifying and offer and particle size distribution.
The invention provides dispersion of polymer particle stable under all pH value condition.Especially, these dispersions are stable under the conditions of low ph value (e.g., less than 7).In one embodiment of the invention, this dispersion of polymer particle has the pH less than 7.Find that this dispersion is also even stable under the conditions of low-down pH value (in the grade of about 3).Therefore, the present invention has been reduced or eliminated the pH sensitivity of typical latex formulation.Therefore, pH value need not to be maintained at a specific alkalescence value, and do not require buffer agent to keep or reach required pH.
These stable emulsions are particularly effective in the application of such as paint, coating or adhesive composition.Therefore, a kind of paint, coating or adhesive composition can include dispersion of polymer particle described here, this dispersion includes polymer that a kind of emulsion is polymerized and a kind of macromole evocating agent, and this macromole evocating agent includes being in the form reacted, monomer a kind of hydrophilic, that pH is insensitive on the polymer that is covalently bonded to the polymerization of this emulsion.
This paint, coating or adhesive composition can also include at least one other paint, coating or adhesive component.That paint component is known to those skilled in the art and may include that such as pigment, binding agent, solvent, catalyst, thickening agent, stabilizer, emulsifying agent, adjusting material (texturizer), help binder, UV stabilizer, leveling agent (agent of frosting), Biocide etc..Coating composition be the most also known to and may include that such as defoamer, lubricant, plasticizer etc..Adhesive component be also known to and may include that such as defoamer, curing catalysts, dissociation catalyst, filler, rheology modifier, antioxidant, pigment, viscosifier, plasticizer, help binder, stabilizer, fire retardant etc..These binding agents can be mixed by a kind of usual manner and any convenience point in preparing this latex maybe this paint, coating or adhesive composition.
In one embodiment of the invention, a kind of method for manufacturing dispersion of polymer particle includes making at least one monomer and a kind of active macromolecules initiator carry out reacting and not having surfactant to complete the polyreaction of this at least one monomer in a kind of aqueous medium, and wherein this active macromolecules initiator includes that the monomer a kind of hydrophilic, that pH is insensitive being in the form being polymerized and this at least one monomer are a kind of ethylene linkage unsaturated monomer.
As used herein, " surfactant-free " or " not having surfactant " is intended to not or the surfactant of only trace.In other words, in this reaction medium, a kind of surfactant is the most on purpose added.
Any suitable technology as known in the art can be used to form this macromole evocating agent.In one embodiment of the invention, this macromole evocating agent is formed by carrying out a kind of controlled radical polymerization of monomer that this is hydrophilic, that pH is insensitive and a kind of alkoxyamine compound including a nitrogen-oxygen key.
This controlled Raolical polymerizable can be that a kind of NO free radical regulates and controls (NMP) or reversible-addition-fracture-transfer (RAFT) polyreaction.The polyreaction (NMP) of NO free radical regulation and control be to those skilled in the art known to and the number of free radical that allows this propagation be limited in the level allowing controlled fusion.Reversible-addition-fracture-transfer (RAFT) polyreaction is also well known to those of ordinary skill in the art and is effective, because the free radical intermediate of stabilisation re-introduces and a kind of can terminate, with limited, the group that reaction causes with one or more monomers again or breeds.
This macromole evocating agent can also be prepared with a kind of reversible-addition-fracture-transfer (RAFT) reagent.RAFT reagent may include that such as N, N '-azo double (isopropyl cyanide) (AIBN), dibenzyl trithiocarbonate (DBTTC), 1-phenyl acrylate-2-base phenyl methyl-carbithionic acid ester；1-phenyl ethyl phenyl methyl-carbithionic acid ester, cumyl phenyl methyl-carbithionic acid ester, 2-phenyl acrylate-2-base dithiobenzoic acid ester；1-phenyl acrylate-2-base p-bromo dithiobenzoic acid ester；1-phenylethyl dithiobenzoic acid ester；2-cyano group acrylate-2-base dithiobenzoic acid ester；4-cyanopentanoic acid dithiobenzoic acid ester；1-Acetoxvethyl dithiobenzoic acid ester；Six (thiobenzoyl sulphomethyl) benzene；Isosorbide-5-Nitrae-bis-(thiobenzoyl sulphomethyl) benzene；1,2,4,5-tetra-(thiobenzoyl sulphomethyl) benzene；Ethoxycarbonylmethyl group methyl-carbithionic acid ester；2-(carbethoxyl group) acrylate-2-base dithiobenzoic acid ester；Tert-butyl group dithiobenzoic acid ester；Isosorbide-5-Nitrae-bis-(2-thiobenzoyl sulfur is for acrylate-2-yl) benzene；4-cyano group-4-(thiobenzoyl sulfur generation) valeric acid；Dibenzyl trithiocarbonate；Carboxymethyl dithio benzoate；S-benzyl diethoxy phosphinyl dithio formate；2,4,4 ,-trimethyl amyl-2-base dithiobenzoic acid ester；2-(ethoxycarboxy) acrylate-2-base dithiobenzoic acid ester；2-phenyl acrylate-2-base dithio naphthalate；2-phenyl the third 2-base chloro dithiobenzoic acid ester.
Any polyreaction described here can also include other suitable compositions.Such as, acid, salt, chain-transferring agent, initiator, reducing agent and controlling agent can also be used in preparing this active macromolecules initiator or this dispersion of polymer particle, and they can be mixed in any suitable moment.
According to another embodiment of the invention, a kind of method for forming this latex includes:
A () makes a kind of monomer hydrophilic, that pH is insensitive and a kind of alkoxyamine compound including a nitrogen-oxygen key carry out being reacted to form a kind of active macromolecules initiator；
B a kind of water-based emulsion of () preparation, this water-based emulsion includes at least one monomer, this active macromolecules initiator, but not including that surfactant；And
C this emulsion is kept under the polymerization conditions to provide a kind of latex comprising scattered polymer beads by ().
Monomer that this is hydrophilic, that pH is insensitive and this alkoxyamine compound such as react in water, to form a kind of macromole evocating agent.This active macromolecules initiator can be formed in a kind of aqueous or nonaqueous solvent.If this active macromolecules initiator is to be formed in a kind of non-aqueous solvent, then can this activity be dissolved in a kind of aqueous solvent according to initiator after a while.In an exemplary embodiment, this active macromolecules initiator (such as water) in a kind of aqueous medium is formed, to provide a kind of active macromolecules initiator solution.
Any suitable condition can be selected to be effectively formed this macromole evocating agent.For example, it is possible to by along with continuous print stirring this mixture is heated to 90 DEG C or higher than its (e.g., from about 90 DEG C-130 DEG C) between a temperature carry out initiated polymerization.Polyreaction is made to continue by being maintained at by this mixture at a temperature of selected, until having reached this or these monomers desired conversion ratio to polymer.Such as, this is probably the grade at several hours.
Need not be purified or separate before being introduced in water-based emulsion by this active macromolecules initiator.In other words, this mixture that this obtained from step (a) can be comprised active macromolecules initiator and one or more monomers unreacted is directly added into step (b).Therefore, it can directly react this aqueous active macromole evocating agent with this monomer mixture according to obtained (such as, containing unreacted AMPS monomer).
It is prepared for including at least one monomer, this active macromolecules initiator formed in step (a) and a kind of solvent but does not include a kind of emulsion of surfactant.This emulsion is kept under the polymerization conditions to provide a kind of latex comprising scattered polymer beads.Any suitable condition can be selected to come effectively this mixture is converted into a kind of latex.Such as, enough to cause the value of polyreaction to use this macromole evocating agent.As set forth above, it is possible to by the mixture of this emulsifying being heated to along with continuous stirring at about 90 DEG C or causing this polyreaction higher than a temperature between its (such as, 90 DEG C-130 DEG C).Polyreaction is made to continue by being maintained at by the mixture of this emulsifying at a temperature of selected, until having reached the conversion to latex.
Forming this active macromolecules initiator or during forming these dispersion of polymer particle, the mode of these polyreaction compositions of this merging can be changed by different known feed process, such as continuous print monomer adds, cumulative monomer adds or adds the monomer (i.e., in batches) of whole amount in single charging.The whole amount of this aqueous medium with polyreaction additive can be present in this polymerization container before introducing monomer, or alternately, can add this aqueous medium or its any part in this polymerization process continuously or increasingly.
Any suitable method can be used to process this emulsion further.It is, for example possible to use technology well known by persons skilled in the art is quenched or pursues (chase) this dispersion of polymer particle, this can shorten the response time and make product have low residual monomer level.In other words, should " pursuit " step can be used to consume unreacted monomer.It is, for example possible to use (such as t-butyl hydroperoxide and sodium sulfoxylate formaldehyde) is polymerized remaining monomer by the water soluble starter of routine such as potassium peroxydisulfate or initiator/reducing agent (" oxidoreduction ").Additionally, add reducing agent and can destroy this controlling agent, therefore gather way while reducing the controlled character of this polyreaction.
After polymerisation, by adding water or by removing water (such as by distillation), the solids content of the waterborne polymeric latex generated can be adjusted to desired level.If desired, these polymer beads can be reclaimed from this aqueous dispersion.The size of these polymer beads may change.Suitable granularity can be directly realized by from this polyreaction.Screening gained latex can also be used to remove bigger granule or make size distribution narrow.
Example
Example 1: prepare the latex of the surfactant-free of poly-(AMPSNa) macromole evocating agent of 3kg/mol and poly-(AMPSNa-b-BA-b-BA/MMA/St)
Weigh in the stainless steel reactor that following component adds a 2L: the 50wt%AMPS-Na (aqueous) of 389.29g, 2.265g SG1,481.515g deionized water, 24.805g BB-MA are (from Arkema Inc at Philadelpha, the branch company of PA can get, 6.50x10-2Mole, target Mn≈ 3.0kg/mol) and the 20wt%NaOH (aqueous) of 17.296g.This mixture is diluted and with nitrogen degasification 10 minutes with 178.71g deionized water.Under agitation this mixture is heated 4 hours at 95 DEG C-105 DEG C.Collect this product (AMPSNa of about 95%cv).The most i.e. use this water macromole evocating agent solution (pAMPSNa or the AMPSNa of polymerization).
653.2g deionized water, 2.42g sodium carbonate and 80.4gp (AMPSNa) macromole evocating agent aqueous solution is added in the stainless steel reactor of a 2L.16.8g butyl acrylate (BA) is added in this uniform solution.Under agitation this mixture is blasted nitrogen, then heat 2 hours (95%cvBA) at 100 DEG C.Gained latex is the solid with low granularity of about 4.8%.
Under agitation, in the above-mentioned latex of 752g, 424.2g BA, 35.0g styrene, 224.0g methyl methacrylate (MMA) are added.Before the radical initiator adding one or more routines carrys out " pursuit " residual monomer, this polymer is made to carry out reacting the MMA conversion ratio reaching 92%.Add to this latex a kind of containing 3.22g sodium sulfoxylate formaldehyde with the solution of 32.2g deionized water, and keep 15 minutes under the conditions of 100 DEG C, be subsequently added 3.79g n octylmercaptan, followed by 1.89g t-butyl hydroperoxide and the deionized water of 16.5g.Make this polymer react 2 hours at 108 DEG C, reach the monomer conversion of 99+%.
Example 2: prepare the latex of the surfactant-free of 2.8kg/mol poly-(hydroxyethyl acrylate) and poly-(hydroxyethyl acrylate-b-MMA)
It is prepared for a kind of nonionic the first block by hydroxyethyl acrylate.Make the BB-MA (1.79x10 of 5.0400g hydroxyethyl acrylate (HEA), 9.949g deionized water, the sodium carbonate of 0.174g and 0.682g-3Mole, target Mn≈ 2.8kg/mol) polyase 13 hour (98%cv HEA) under the conditions of 90 DEG C.
P (hydroxyethyl acrylate) aqueous solution of this low-molecular-weight of 1.2626g is joined in a vial with 11.424g deionized water and 3.514g MMA.Make this mixture be polymerized 1 hour at 100 DEG C, reach the MMA conversion ratio of 65%.Although granularity is bimodal, but this latex is stable.
Example 3: the latex of the surfactant-free of a kind of poly-(AMPSNa-b-BA-b-MMA/BA-gradient) triblock copolymer of preparation
P (AMPSNa) macromole evocating agent using a kind of 2kg/mol is prepared for pBA first block of 50kg/mol.Load in a 2L Parr high-pressure reactor: 257.7g deionized water, 0.43g NaHCO3, 14.4wt%p (AMPSNa) macromole evocating agent aqueous solution (5.1g p (AMPSNa), the 2.54x10 of 35.3g-3Mole, Mn≈ 2.0kg/mol) and 149.5g butyl acrylate (BA).This reactor is sealed, shake, blasts nitrogen and be heated to 120 DEG C, until obtaining the BA conversion ratio of 85%.Next by this reactor cooled to room temperature.This latex have 28.4% solid and an intensity mean particle size DI=130nm.
It is prepared for this p (MMA-co-BA) gradient copolymer the second block as follows.80.5g methyl methacrylate is added in above latex.This reactor is sealed, shake, blasts nitrogen and be heated to 105 DEG C, until obtaining the MMA conversion ratio of 69.5% and the conversion ratio of the residue BA of 51%.At this moment, this latex has solid and the D of 36.9%I=143.1nm.When this reactor is at 105 DEG C, add 0.61g sodium sulfoxylate formaldehyde and a solution of 10.0g deionized water through peristaltic pump to this reactor.After 1 hour, the conversion ratio of all monomers is ＞ 99+%.Final latex is solid and the D of 42.6%I=158nm.The composition (in terms of wt.%, based on GC conversion ratio) of block copolymer is 2.2%p (AMPSNa), 55.6%pBA and 42.2%p (MMA80.3 %/BA19.7 %)。
Example 4: the latex of the surfactant-free of a kind of poly-(AMPSNa-b-BA-b-MMA/BA-gradient) triblock copolymer of preparation
P (AMPSNa) macromole evocating agent using a kind of 2kg/mol is prepared for pBA first block of 3kg/mol.Load in a 2L Parr high-pressure reactor: 853.3g deionized water, 3.57g NaHCO3, 42.4wt%p (AMPSNa) macromole evocating agent aqueous solution (16.8gp (AMPSNa), the 5.60x10 of 0.14g NaOH, 39.80g-3Mole, Mn≈ 2.0kg/mol) and 16.8g butyl acrylate.This reactor is sealed, shake, blasts nitrogen and heat 1 hour at 100 DEG C, cause the conversion of BA.By this reactor cooled to room temperature.This latex have 2.5% solid and an intensity mean particle size DI=373nm.
It is prepared for this p (MMA-co-MAA-co-BA gradient copolymer) the second block as follows.246.8g methyl methacrylate, 10.7g methacrylic acid (MAA) and 428.54g butyl acrylate is added to above latex.This reactor is sealed, shake, blasts nitrogen and heat 10 hours at 108 DEG C, heat 12 hours at 110 DEG C subsequently, thus obtain the BA conversion ratio (the total monomer conversion ratio of 91%) of the MMA conversion ratio of 97.5%, the MAA conversion ratio of 100% and 86.7%.By reactor cooled to room temperature.This latex has solid and the D of 38.8%I=260nm.
" pursuit " residual monomer is carried out by conventional radical initiator.1.42g n octylmercaptan, 1.10g sodium sulfoxylate formaldehyde and a solution of 10.8g deionized water is added in above latex.This reactor is sealed, shake, blasts nitrogen and be heated to 70 DEG C, after this, add 0.7g t-butyl hydroperoxide and a solution of 6.0g deionized water through peristaltic pump to this reactor.At 70 DEG C after 1 hour, the conversion ratio of all monomers is ＞ 99+%.Final latex has solid and the D of 40.6%I=259nm.The composition (in terms of wt.%, based on GC conversion ratio) of block copolymer is 2.6%p (AMPSNa), 2.6%pBA and 94.9%p (MMA38.6 %/MAA1.7 %/BA59.6 %)。
Example 5: the latex of the surfactant-free of a kind of poly-(AMPSNa-b-BA-b-MMA/BA-gradient) triblock copolymer stability at a low ph
One aliquot of the latex in HCl (aqueous) titration example 3 with 0.8%, until pH ＜ 3.
Example 6: prepare the latex of the surfactant-free of 5kg/mol poly-(methacrylate-co-AMPSNa) and poly-(HEMA/AMPS)-b-PMMA
Sulphonic acid ester/hydroxyl first block of a kind of mixing it is prepared for by methacrylate.Make 2.153g methacrylate (HEMA), the 50wt%AMPS-Na (aqueous) of 12.7742g, 0.021g SG1,1.580g deionized water and the BB-MA (1.79x10 of 0.649g-3Mole, target Mn≈ 5kg/mol) at 85 DEG C, it is polymerized 2 hours (98%cv HEMA).
The aqueous solution of the above-mentioned low-molecular-weight of 1.7188g is joined in a vial equipped with 11.1949g deionized water and 5.4146g MMA.Make this mixture be polymerized 2 hours at 90 DEG C, reach the MMA conversion ratio of 33%.Di=152, has narrow distribution (1.17).
Although being shown in which and described the preferred embodiment of the present invention, it is to be understood that this type of embodiment is only through what way of example provided.Those of ordinary skill in the art will appreciate that numerous variant, change and replace the spirit without departing from the present invention.Therefore, it is expected that claims cover just like the such variant fallen within the scope and spirit of the invention.
Claims (22)
1. the polymer beads not having surfactant stable in the aqueous medium of all pH value
Dispersion, including a kind of emulsion polymerization polymer and be covalently bonded to this emulsion polymerization polymer on
A kind of active macromolecules initiator,
Wherein this active macromolecules initiator includes the AMPS (2-acrylamido-2-methyl-prop sulphur being polymerized
Acid) or its salt；And
The polymer of this emulsion polymerization includes at least one other ethylene linkage insatiable hunger being in the form being polymerized
And monomer；
Wherein, described dispersion of polymer particle does not require buffer agent.
A kind of dispersion of polymer particle the most according to claim 1, wherein the polymerization of this emulsion is poly-
Compound is selected from lower group, and the composition of this group is: based on (methyl) acrylate, styrene, (methyl) acryloyl
Amine, the polymer of (methyl) acrylonitrile, and their mixture.
A kind of dispersion of polymer particle the most according to claim 1, wherein the polymerization of this emulsion is poly-
Compound includes a kind of homopolymer or copolymer, wherein this copolymer be a kind of statistics, random, block,
Or the copolymer of gradient.
A kind of dispersion of polymer particle the most according to claim 1, wherein this polymer beads divides
A prose style free from parallelism has the pH less than 7.
5. paint, coating or an adhesive composition, including one according to claim 1
Dispersion of polymer particle.
6. paint, coating or an adhesive composition, including one according to claim 1
Dispersion of polymer particle and paint, coating or adhesive composition that at least one is other.
A kind of dispersion of polymer particle in an aqueous medium the most according to claim 1, wherein
This active macromolecules initiator and at least one monomer carry out reacting and forming one and have formula
R-{[(A)x(B)y]-[(C)m]p-Y}N or 1Polymer, wherein A is this monomer hydrophilic, that pH is insensitive,
B is a kind of comonomer, and C is the undersaturated monomer of at least one ethylene linkage, and Y is an end group, x >=1,
Y >=0, m >=1, n >=2, and p >=1, if wherein p > 1, the most each C section has a kind of different
Composition, and A and B can occur in this active macromolecules initiator in any order or sequence, and
And R has with following formula (I) or (III):
Wherein R1And R3Identical or different, represent the alkane of straight or branched that a carbon number having is from 1 to 3
Base；R2Represent a hydrogen atom or carbon number having from 1 to 8 straight or branched alkyl,
One phenyl, an alkali metal ion or an ammonium ion；And Z represents an aryl or one
There is formula Z1-[X-C(O)]nGroup, wherein Z1Representing a kind of polyfunctional structure, wherein X is that an oxygen is former
Son, a nitrogen-atoms with a carbon-based group, a hydrogen atom or a sulphur atom.
A kind of dispersion of polymer particle in an aqueous medium the most according to claim 7, wherein
Y is to have with the R' of following formula (II):
9. one kind is used in the polymer particles not having surfactant stable in the aqueous medium of all pH value
The AMPS (2-acrylamide-2-methylpro panesulfonic acid) being polymerized in grain dispersion or its salt；
Wherein, described dispersion of polymer particle does not require buffer agent.
10. the polymerization stablizing, not having surfactant for manufacture in the aqueous medium of all pH value
The method of composition granule dispersion, including:
At least one monomer and a kind of active macromolecules initiator is made to react in a kind of aqueous medium and not have
There is surfactant to complete the polyreaction of this at least one monomer, wherein this active macromolecules initiator
Including the AMPS (2-acrylamide-2-methylpro panesulfonic acid) being polymerized or its salt, and this at least one
Monomer is a kind of undersaturated monomer of ethylene linkage；Wherein, described dispersion of polymer particle does not require buffer agent.
11. a kind of methods according to claim 10, wherein this at least one monomer is selected from lower group, should
Group composition be: (methyl) acrylate, styrene, (methyl) acrylamide, (methyl) acrylonitrile, with
And their mixture.
12. a kind of methods according to claim 10, wherein by having with following formula (IV) or (V)
A kind of alkoxyamine compound in the presence of carry out one of monomer that this is hydrophilic, that pH is insensitive in advance and be subject to
The Raolical polymerizable of control forms this active macromolecules initiator.
Wherein R1And R3Identical or different, represent the alkane of straight or branched that a carbon number having is from 1 to 3
Base；R2Represent a hydrogen atom, carbon number having from 1 to 8 straight or branched alkyl,
One alkali metal ion of one phenyl or an ammonium ion；Z represent an aryl or one there is formula
Z1-[X-C(O)]nGroup, wherein Z1Representing a kind of polyfunctional structure, wherein X is oxygen atom, a band
There are a nitrogen-atoms of a carbon-based group, a hydrogen atom or a sulphur atom；And n >=2.
13. a kind of methods according to claim 12, wherein this macromole evocating agent is in a kind of aqueous
Medium is formed.
14. a kind of methods according to claim 12, wherein this controlled Raolical polymerizable is one
Plant NO free radical regulates and controls or reversible-addition-fracture-transfer (RAFT) polyreaction.
15. a kind of methods according to claim 12, wherein this alkoxyamine compound is N-(2-first
Base propyl group)-N-(1-diethylphosphoryl base-2,2-dimethyl propyl)-O-(2-carboxyl acrylate-2-yl) azanol.
16. a kind of methods according to claim 12, wherein, list that pH insensitive hydrophilic at this
During the controlled radical polymerization of body and this alkoxyamine compound, add a kind of NO free radical chemical combination
Thing.
17. to go out a kind of method described in 12 according to right, and the monomer wherein making a kind of non-sulfonated is hydrophilic with this
, the monomer copolymerization that pH is insensitive.
18. a kind of methods according to claim 12, wherein this active macromolecules initiator is by one
Prepared by reversible-addition-fracture-transfer (RAFT) reagent.
The method of 19. 1 kinds of latex comprising scattered polymer beads for formation, including:
Make 2-acrylamide-2-methylpro panesulfonic acid and a kind of alkoxyamine chemical combination including a nitrogen-oxygen key
Thing carries out being reacted to form the AMPS's (2-acrylamide-2-methylpro panesulfonic acid) or its salt for being polymerized
Macromole evocating agent；
A kind of water-based emulsion of preparation, this water-based emulsion includes that at least one monomer and this active macromolecules cause
Agent, but do not include a kind of surfactant；And
This emulsion is maintained under the polymerization conditions with provide a kind of in the aqueous medium of all pH value steady
The fixed latex comprising scattered polymer beads；
Wherein, described dispersion of polymer particle does not require buffer agent.
20. a kind of methods according to claim 19, wherein this 2-acrylamido-2-methyl-prop sulphur
The reaction of acid and this alkoxyamine compound is in a kind of aqueous medium, at a temperature of equal to or higher than 90 DEG C
Occur.
21. a kind of method according to claim 19, wherein this emulsion polymerization condition includes heating
To equal to or higher than 90 DEG C.
22. a kind of methods according to claim 19, are wherein introducing this breast by this active macromolecules initiator
Need not be purified or separate before in liquid.
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| DE10153932A1 (en) | 2001-11-06 | 2003-05-22 | Basf Ag | Aqueous synthetic resin preparation |
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| US8338518B2 (en) | 2005-06-10 | 2012-12-25 | Arkema Inc. | Aqueous process for making a stable fluoropolymer dispersion |
| US20070142513A1 (en) | 2005-12-21 | 2007-06-21 | Daikin Industries, Ltd. | Surfactant, method of producing a fluoropolymer, fluoropolymer aqueous dispersion |
| US7671152B2 (en) | 2005-12-22 | 2010-03-02 | The Goodyear Tire & Rubber Company | Surfactantless synthesis of amphiphilic cationic block copolymers |
| US20080108749A1 (en) | 2006-11-07 | 2008-05-08 | Nanomax Technology Company Limited | Fluoropolymer nanoemulsions |
| FR2927252B1 (en) | 2008-02-12 | 2010-04-23 | Oreal | OIL-IN-WATER EMULSION CONTAINING AN AMPHIPHILE POLYMER |
| FR2931153B1 (en) * | 2008-05-19 | 2010-05-28 | Arkema France | PROCESS FOR PREPARING A DISPERSION OF POLYMERIC PARTICLES IN AQUEOUS MEDIUM |
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| Nitroxide-MediatedControlled/LivingFree-RadicalSurfactant-Free Emulsion Polymerization of Methyl Methacrylate Using a Poly(methacrylic acid)-Based Macroalkoxyamine Initiator;Charlotte Dire,et al.;《Macromolecules》;20081215;第95-103页 * |
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